US20070240635A1 - Crucible for The Crystallization of Silicon - Google Patents
Crucible for The Crystallization of Silicon Download PDFInfo
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- US20070240635A1 US20070240635A1 US11/587,081 US58708105A US2007240635A1 US 20070240635 A1 US20070240635 A1 US 20070240635A1 US 58708105 A US58708105 A US 58708105A US 2007240635 A1 US2007240635 A1 US 2007240635A1
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- crucible
- intermediate layer
- silicon
- layer
- silica
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/10—Crucibles or containers for supporting the melt
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
- Y10T117/10—Apparatus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
- Y10T117/10—Apparatus
- Y10T117/1024—Apparatus for crystallization from liquid or supercritical state
- Y10T117/1032—Seed pulling
Definitions
- the invention relates to a crucible for the crystallization of silicon and to the preparation and application of release coatings for crucibles used in the handling of molten materials that are solidified in the crucible and then removed as ingots, and more particularly to release coatings for crucibles used in the solidification of polycrystalline silicon.
- Silicon in its molten state will react with the silica crucible that is in contact with it.
- Molten silicon reacts with silica to form silicon monoxide and oxygen. Oxygen will contaminate the silicon.
- Silicon monoxide is volatile, and will react with the graphite components inside the furnace. Silicon monoxide reacts with graphite to form silicon carbide and carbon monoxide. The carbon monoxide will then react with the molten silicon, forming additional volatile silicon monoxide and carbon. Carbon will contaminate the silicon.
- Silicon can also react with the various impurities contained in the silica crucible (iron, boron, aluminum, ).
- the reaction between silica and silicon promotes adhesion of the silicon to the crucible.
- This adhesion combined with a difference in coefficients of thermal expansion between the two materials, creates stress in the silicon ingot, causing it to crack on cooling.
- a release coating applied to the inside of the crucible in the area of contact with the ingot can prevent the reaction between silicon and silica that leads to ingot contamination and cracking.
- the release coating must be thick enough to prevent the silicon from reacting with the silica crucible, and must not adversely contaminate the silicon either by itself or from contaminants within it.
- U.S. Pat. No. 4,741,925 describes a silicon nitride coating for crucibles applied by chemical vapor deposition at 1250° C. while WO-A1-2004/053207 discloses a silicon nitride coating applied by plasma spraying.
- U.S. Pat. No. 3,746,569 discloses the pyrolysis formation of a silicon nitride coating on the walls of a quartz tube.
- U.S. Pat. No. 4,218,418 describes a technique of forming a glass layer inside a silica crucible by rapid heating to prevent cracking of silicon during melt-processing.
- 3,660,075 discloses a coating of niobium carbide or yttrium oxide on a graphite crucible for melting fissile materials.
- the niobium carbide is applied by chemical vapor deposition, while the yttrium oxide is applied as a colloidal suspension in an aqueous inorganic solution.
- Prior art references include specific references to powdered mold release agents for application to crucibles in the directional solidification of silicon.
- the use of chemical vapor deposition, solvent evaporation, high-temperature flame treatment, and other expensive and complex means are mentioned for application of crucible coatings.
- References are made to specific binders and solvents.
- References are made to mixing, spraying, or brushing for slurries of powdered coatings.
- This silicon nitride release coating itself can lead to problems.
- the thickness of the silicon nitride coating necessary to prevent the silicon from reacting with the silica crucible is quite important (about 300 ⁇ m) making thereby the coating operation expensive and time consuming.
- this silicon nitride coating is mechanically weak and can peel or flake off during or even before use. It is therefore recommended to apply this coating at the very last moment before use, i.e., at the end user facilities, leaving thereby the burden of applying this thick coating to the end user.
- a crucible for the crystallization of silicon comprising a) a base body comprising a bottom surface and side walls defining an inner volume; b) an intermediate layer comprising 50 to 100 wt. % of silica at the surface of the side walls facing the inner volume; and c) a surface layer comprising 50 to 100 wt. % silicon nitride, up to 50 wt. % of silicon dioxide and up to 20 wt. % of silicon on the top of the intermediate layer.
- the intermediate layer comprising 50 to 100 wt. % of silica at the surface of the side walls is extremely resistant and easy to manufacture. Since there is no problem of peeling or flaking off with this intermediate layer, it can be prepared before reaching the end user facilities so that the end user only needs to provide a thin surface layer which is faster and cheaper to coat. Moreover, it has been surprisingly discovered that this intermediate layer tremendously increases the adhesion of the surface layer.
- the strength of the intermediate layer is voluntarily limited so that the adhesion of the intermediate layer to the surface layer and/or the base body is lower than the adhesion of the surface layer to a silicon ingot. Consequently, during the crystallization of the silicon ingot—if for any reason—the silicon ingot adheres to the surface layer, the intermediate layer will delaminate under the effect of the stress generated by the cooling of the ingot. Thereby, only the coating of the crucible is destroyed, leaving the silicon ingot in perfect shape.
- One way of limiting the strength of the intermediate layer is to act on the porosity of said layer.
- the porosity can be determined by the granulometry of the particles included in the layer (a majority of large particles will result in a high porosity). Another possibility is to include in the composition a material that will confer or generate the required porosity. For example, the use of alumina microbubbles (FILLITE) of silico-aluminate fibers will confer the required porosity. Carbonaceous materials such as resins or carbon which will pyrolyse without residue but with the production of fine carbon dioxide bubbles during firing will generate the required porosity as well.
- FILLITE alumina microbubbles
- Carbonaceous materials such as resins or carbon which will pyrolyse without residue but with the production of fine carbon dioxide bubbles during firing will generate the required porosity as well.
- This coating is that it can be applied on various crucible materials so that the end user which receives a crucible with a silica containing intermediate layer does not need to develop particular and different procedures to coat various materials.
- the intermediate layer can be applied on quartz, fused silica, silicon nitride, SiAlON, silicon carbide, alumina or even graphite crucibles.
- the intermediate layer has a thickness of 50 to 300 ⁇ m so as to provide the majority of the thickness necessary to prevent reaction of the silicon with the crucible, and contamination of the silicon from contaminants within it.
- the intermediate layer can comprise any material which, after firing, will be stable and will not react with silicon.
- Alumina or silico-aluminate materials are particularly suitable. Carbonaceous materials that will pyrolyse during firing can also be used for certain applications.
- the intermediate layer can comprise a non-organic (such as colloidal silica) and/or organic (such as an organic resin like polyethylene glycol, polyvinyl alcohol, polycarbonate, epoxy, carboxymethylcellulose) binder.
- a non-organic such as colloidal silica
- organic such as an organic resin like polyethylene glycol, polyvinyl alcohol, polycarbonate, epoxy, carboxymethylcellulose
- the amount of the organic and non organic binder incorporated into the composition depends upon the application requirements (strength of the unfired coating, etc.).
- the coating comprises from 5 to 20 wt. % of non-organic binder and up to 5 wt. % of organic binder.
- the intermediate layer is applied in water or in solvent by spraying or brushing. Preferably by spraying in a water based system comprising an appropriate amount of water to permit the suspension of the whole composition.
- the crucible comprises a further layer (a second intermediate layer) on the top of the intermediate layer.
- This further layer comprises up to 50 % by weight of silicon nitride, the remainder consisting essentially of silicon dioxide.
- This further layer improves the compatibility between the surface layer and the first intermediate layer and strongly improves its adhesion.
- this further layer will have a thickness of up to 200 ⁇ m, preferably of 50 to 100 ⁇ m.
- the surface layer will have a thickness of 50 ⁇ m to 500 ⁇ m, preferably of 200 to 500 ⁇ m. To avoid any contamination, it is essential that the surface layer be of very high purity with a ultra-low carbon content. Typically, the surface layer will comprise 50 to 100 wt. % of Si 3 N 4 , up to 50 wt. % of SiO 2 and up to 20 wt. % of silicon. Usually, the surface layer will be applied by spraying or brushing, preferably by spraying. In a preferred embodiment of the process according to the invention, the step of applying the coating is followed by a heating step at a temperature and for a duration appropriate to calcinate substantially all the organic compound present in the coatings. It can be noted that when an intermediate layer according to the invention is used, the thickness of the surface layer can be largely reduced without impairing the properties of the coating (adhesion properties).
- FIGS. 1 and 2 show cross-sections of crucibles according to the invention.
- the crucible is designated with reference number 1 . It comprises a base body 2 comprising a bottom surface 21 and side walls 22 which define an inner volume for the crystallization of silicon.
- the crucible comprises an intermediate layer 3 which is comprised of up to 100 wt. % of silica at the surface of the side walls 22 facing the inner volume.
- the crucible comprises a further intermediate layer 31 comprising up to 50 wt. % of Si 3 N 4 , the remainder consisting essentially of SiO 2 .
- a further intermediate coating is not present on FIG. 1 .
- the crucible 1 further comprises a surface layer 4 comprising Si 3 N 4 .
- intermediate layers TABLE I • Intermediate layer A B C D E F G Colloidal 25 30 30 15 silica** Fume silica 20 20 10 10 20 ( ⁇ 1 ⁇ m)** Silica grains 100 40 40 6 10 65 (10-20 ⁇ m)** Silica grains 20 65 60 60 (20-44 ⁇ m)** Silica grains 40 20 4 (45-100 ⁇ m)** Deionized +50 +50 water** Deionized +70 +66 +50 +45 +60 water + Binder** (PVA 10 wt.
- the preferred examples are those of compositions C and G, G being the most preferred.
- Further intermediate layer TABLE II Further intermediate layer IA IB IC Fume silica ( ⁇ 1 ⁇ m)** 20 Silica grains (10-20 ⁇ m)** 60 40 Silica grains (20-44 ⁇ m)** 60 Deionized water** +60 Deionized water + Binder** +70 +80 (PVA 10 wt. %)) Silicon nitride powder** 40 40 40 Thickness of the layer ( ⁇ m) 50 75 100 Roughness ( ⁇ m) 10 8 5 **(wt. %) The preferred composition is the one of example IB.
- Examples of surface layer TABLE III Surface layer SA SB SC SD Colloidal silica** 5 Silica grains (10-20 ⁇ m)** 5 Deionized water** +55 Deionized water + Binder** +70 +65 (PVA 10 wt. %) Silicon nitride powder** 100 100 80 85 Si** 15 10 Thickness of the layer ( ⁇ m) 100 200 200 300 Roughness ( ⁇ m) 5 5 ⁇ 5 5 Adhesion*** (kPa) 241 827 965 827 **(wt. %) ***with a substrate corresponding to intermediate layer G Preferred compositions are SA and SB, the most preferred composition being SB.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Crucibles And Fluidized-Bed Furnaces (AREA)
- Silicon Compounds (AREA)
- Glass Melting And Manufacturing (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
- Mold Materials And Core Materials (AREA)
Abstract
Description
- The invention relates to a crucible for the crystallization of silicon and to the preparation and application of release coatings for crucibles used in the handling of molten materials that are solidified in the crucible and then removed as ingots, and more particularly to release coatings for crucibles used in the solidification of polycrystalline silicon.
- Crucibles of silica (either of fused-silica or of quartz) are typically used in solidification of polycrystalline silicon. Silica is chosen primarily for high-purity and availability. There are problems in using silica, however, as a crucible for the production of silicon by this method.
- Silicon in its molten state will react with the silica crucible that is in contact with it. Molten silicon reacts with silica to form silicon monoxide and oxygen. Oxygen will contaminate the silicon. Silicon monoxide is volatile, and will react with the graphite components inside the furnace. Silicon monoxide reacts with graphite to form silicon carbide and carbon monoxide. The carbon monoxide will then react with the molten silicon, forming additional volatile silicon monoxide and carbon. Carbon will contaminate the silicon. Silicon can also react with the various impurities contained in the silica crucible (iron, boron, aluminum, ).
- The reaction between silica and silicon promotes adhesion of the silicon to the crucible. This adhesion, combined with a difference in coefficients of thermal expansion between the two materials, creates stress in the silicon ingot, causing it to crack on cooling. It is known in the art that a release coating applied to the inside of the crucible in the area of contact with the ingot can prevent the reaction between silicon and silica that leads to ingot contamination and cracking. To be effective, the release coating must be thick enough to prevent the silicon from reacting with the silica crucible, and must not adversely contaminate the silicon either by itself or from contaminants within it.
- A variety of materials and techniques are described in the literature, which attempt to solve the problem of reaction and adhesion of the crucible in contact with molten material. For example U.S. Pat. No. 5,431,869 describes a multi-component release agent of silicon nitride and calcium chloride for silicon processing using a graphite crucible.
- U.S. Pat. No. 4,741,925 describes a silicon nitride coating for crucibles applied by chemical vapor deposition at 1250° C. while WO-A1-2004/053207 discloses a silicon nitride coating applied by plasma spraying. U.S. Pat. No. 3,746,569 discloses the pyrolysis formation of a silicon nitride coating on the walls of a quartz tube. U.S. Pat. No. 4,218,418 describes a technique of forming a glass layer inside a silica crucible by rapid heating to prevent cracking of silicon during melt-processing. U.S. Pat. No. 3,660,075 discloses a coating of niobium carbide or yttrium oxide on a graphite crucible for melting fissile materials. The niobium carbide is applied by chemical vapor deposition, while the yttrium oxide is applied as a colloidal suspension in an aqueous inorganic solution.
- Prior art references include specific references to powdered mold release agents for application to crucibles in the directional solidification of silicon. In addition, the use of chemical vapor deposition, solvent evaporation, high-temperature flame treatment, and other expensive and complex means are mentioned for application of crucible coatings. References are made to specific binders and solvents. References are made to mixing, spraying, or brushing for slurries of powdered coatings.
- This silicon nitride release coating itself can lead to problems. The thickness of the silicon nitride coating necessary to prevent the silicon from reacting with the silica crucible is quite important (about 300 μm) making thereby the coating operation expensive and time consuming. Further, this silicon nitride coating is mechanically weak and can peel or flake off during or even before use. It is therefore recommended to apply this coating at the very last moment before use, i.e., at the end user facilities, leaving thereby the burden of applying this thick coating to the end user.
- It would therefore be desirable to provide a silica crucible which does not present the above problems (i.e. which does not require the preparation of a very thick coating at the end user facilities, which is faster and cheaper to produce and which presents a stronger coating with an improved adherence to the walls).
- It has now been found that these problems can be solved with a crucible for the crystallization of silicon comprising a) a base body comprising a bottom surface and side walls defining an inner volume; b) an intermediate layer comprising 50 to 100 wt. % of silica at the surface of the side walls facing the inner volume; and c) a surface layer comprising 50 to 100 wt. % silicon nitride, up to 50 wt. % of silicon dioxide and up to 20 wt. % of silicon on the top of the intermediate layer.
- Indeed, the intermediate layer comprising 50 to 100 wt. % of silica at the surface of the side walls is extremely resistant and easy to manufacture. Since there is no problem of peeling or flaking off with this intermediate layer, it can be prepared before reaching the end user facilities so that the end user only needs to provide a thin surface layer which is faster and cheaper to coat. Moreover, it has been surprisingly discovered that this intermediate layer tremendously increases the adhesion of the surface layer.
- According to an advantageous embodiment of the invention, the strength of the intermediate layer is voluntarily limited so that the adhesion of the intermediate layer to the surface layer and/or the base body is lower than the adhesion of the surface layer to a silicon ingot. Consequently, during the crystallization of the silicon ingot—if for any reason—the silicon ingot adheres to the surface layer, the intermediate layer will delaminate under the effect of the stress generated by the cooling of the ingot. Thereby, only the coating of the crucible is destroyed, leaving the silicon ingot in perfect shape. One way of limiting the strength of the intermediate layer, is to act on the porosity of said layer. The porosity can be determined by the granulometry of the particles included in the layer (a majority of large particles will result in a high porosity). Another possibility is to include in the composition a material that will confer or generate the required porosity. For example, the use of alumina microbubbles (FILLITE) of silico-aluminate fibers will confer the required porosity. Carbonaceous materials such as resins or carbon which will pyrolyse without residue but with the production of fine carbon dioxide bubbles during firing will generate the required porosity as well.
- Another advantage of this coating is that it can be applied on various crucible materials so that the end user which receives a crucible with a silica containing intermediate layer does not need to develop particular and different procedures to coat various materials. The intermediate layer can be applied on quartz, fused silica, silicon nitride, SiAlON, silicon carbide, alumina or even graphite crucibles.
- Advantageously, the intermediate layer has a thickness of 50 to 300μm so as to provide the majority of the thickness necessary to prevent reaction of the silicon with the crucible, and contamination of the silicon from contaminants within it.
- Beside the silica, the intermediate layer can comprise any material which, after firing, will be stable and will not react with silicon. Alumina or silico-aluminate materials are particularly suitable. Carbonaceous materials that will pyrolyse during firing can also be used for certain applications.
- The intermediate layer can comprise a non-organic (such as colloidal silica) and/or organic (such as an organic resin like polyethylene glycol, polyvinyl alcohol, polycarbonate, epoxy, carboxymethylcellulose) binder. The amount of the organic and non organic binder incorporated into the composition depends upon the application requirements (strength of the unfired coating, etc.). Typically, the coating comprises from 5 to 20 wt. % of non-organic binder and up to 5 wt. % of organic binder. Usually, the intermediate layer is applied in water or in solvent by spraying or brushing. Preferably by spraying in a water based system comprising an appropriate amount of water to permit the suspension of the whole composition.
- According to a particular embodiment of the invention, the crucible comprises a further layer (a second intermediate layer) on the top of the intermediate layer. This further layer comprises up to 50 % by weight of silicon nitride, the remainder consisting essentially of silicon dioxide. This further layer improves the compatibility between the surface layer and the first intermediate layer and strongly improves its adhesion. When present, this further layer will have a thickness of up to 200 μm, preferably of 50 to 100 μm.
- Depending upon the application, the surface layer will have a thickness of 50 μm to 500 μm, preferably of 200 to 500 μm. To avoid any contamination, it is essential that the surface layer be of very high purity with a ultra-low carbon content. Typically, the surface layer will comprise 50 to 100 wt. % of Si3N4, up to 50 wt. % of SiO2 and up to 20 wt. % of silicon. Usually, the surface layer will be applied by spraying or brushing, preferably by spraying. In a preferred embodiment of the process according to the invention, the step of applying the coating is followed by a heating step at a temperature and for a duration appropriate to calcinate substantially all the organic compound present in the coatings. It can be noted that when an intermediate layer according to the invention is used, the thickness of the surface layer can be largely reduced without impairing the properties of the coating (adhesion properties).
- The invention will now be described with reference to the enclosed figures which only serve to illustrate the invention and are not intended to limit its scope. Both
FIGS. 1 and 2 show cross-sections of crucibles according to the invention. - On these figures, the crucible is designated with reference number 1. It comprises a
base body 2 comprising abottom surface 21 andside walls 22 which define an inner volume for the crystallization of silicon. The crucible comprises anintermediate layer 3 which is comprised of up to 100 wt. % of silica at the surface of theside walls 22 facing the inner volume. - On
FIG. 2 , the crucible comprises a furtherintermediate layer 31 comprising up to 50 wt. % of Si3N4, the remainder consisting essentially of SiO2. Such a further intermediate coating is not present onFIG. 1 . On both figures, the crucible 1 further comprises a surface layer 4 comprising Si3N4. - The invention will now be illustrated by way of examples according to the invention and comparative examples. In the following tables, the adhesion of the various coatings has been determined in accordance with ASTM D4541 using a POSITEST PULL-OFF ADHESION TESTER (from the firm DEFELSKO Corp.). This tester evaluates the adhesion of the coating by determining the greatest tensile pull off force that it can bear before detaching. I.e., the force required to pull a specified test diameter of coating away from its substrate using hydraulic pressure. The force is expressed in term of pressure (kPa).
- Examples of intermediate layers:
TABLE I • Intermediate layer A B C D E F G Colloidal 25 30 30 15 silica** Fume silica 20 20 10 10 20 (≈1 μm)** Silica grains 100 40 40 6 10 65 (10-20 μm)** Silica grains 20 65 60 60 (20-44 μm)** Silica grains 40 20 4 (45-100 μm)** Deionized +50 +50 water** Deionized +70 +66 +50 +45 +60 water + Binder** (PVA 10 wt. %)) Thickness 300 500 500 150 500 250 200 of the layer (μm) Roughness 5 8 12 ≈5 ≈15 ≈10 5 (μm) Adhesion 1103 345 827 827 1241 1379 1103 (kPa)
**(wt. %)
The preferred examples are those of compositions C and G, G being the most preferred. - Examples of further intermediate layer:
TABLE II Further intermediate layer IA IB IC Fume silica (≈1 μm)** 20 Silica grains (10-20 μm)** 60 40 Silica grains (20-44 μm)** 60 Deionized water** +60 Deionized water + Binder** +70 +80 (PVA 10 wt. %)) Silicon nitride powder** 40 40 40 Thickness of the layer (μm) 50 75 100 Roughness (μm) 10 8 5
**(wt. %)
The preferred composition is the one of example IB. - Examples of surface layer:
TABLE III Surface layer SA SB SC SD Colloidal silica** 5 Silica grains (10-20 μm)** 5 Deionized water** +55 Deionized water + Binder** +70 +65 (PVA 10 wt. %) Silicon nitride powder** 100 100 80 85 Si** 15 10 Thickness of the layer (μm) 100 200 200 300 Roughness (μm) 5 5 ≈5 5 Adhesion*** (kPa) 241 827 965 827
**(wt. %)
***with a substrate corresponding to intermediate layer G
Preferred compositions are SA and SB, the most preferred composition being SB. - Examples of crucible:
TABLE IV Crucible 1 2 3 4 5* 6* Intermediate A B C D — — layer Further IA — IC — — — intermediate layer Surface SA SB SC SD SB SD coating Adhesion of Good Excellent Excellent Good Poor Poor the surface coating
*Comparative example.
It is to be noted that the thickness of the surface layers SB and SD was doubled in examples 5 and 6.
Claims (22)
Applications Claiming Priority (3)
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EP04447105 | 2004-04-29 | ||
EP04447105.0 | 2004-04-29 | ||
PCT/BE2005/000055 WO2005106084A1 (en) | 2004-04-29 | 2005-04-26 | Crucible for the crystallization of silicon |
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EP (1) | EP1745164B1 (en) |
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CN (1) | CN1946881B (en) |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3660075A (en) * | 1969-10-16 | 1972-05-02 | Atomic Energy Commission | CRUCIBLE COATING FOR PREPARATION OF U AND P ALLOYS CONTAINING Zr OR Hf |
US3746569A (en) * | 1969-11-18 | 1973-07-17 | Siemens Ag | Silicon nitride coating on quartz walls for diffusion and oxidation reactors |
US4741925A (en) * | 1987-09-14 | 1988-05-03 | Gte Products Corporation | Method of forming silicon nitride coating |
US5431869A (en) * | 1993-01-12 | 1995-07-11 | Council Of Scientific & Industrial Research | Process for the preparation of polycrystalline silicon ingot |
US6841210B2 (en) * | 2000-05-31 | 2005-01-11 | Heraeus Quarzglas Gmbh & Co., Kg | Multilayer structured quartz glass crucible and method for producing the same |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE962868C (en) | 1953-04-09 | 1957-04-25 | Standard Elektrik Ag | Crucibles for the production of the purest semiconductor material, especially silicon and its use |
JPS54141389A (en) * | 1978-04-27 | 1979-11-02 | Nippon Telegr & Teleph Corp <Ntt> | Crucible used in crystal growing device, manufacture of said crucible and crystal growing method using said crucible |
JPS54157779A (en) * | 1978-06-02 | 1979-12-12 | Toshiba Corp | Production of silicon single crystal |
JPS6018638B2 (en) * | 1979-08-17 | 1985-05-11 | 東芝セラミツクス株式会社 | Silicon single crystal pulling equipment |
JPS57188498A (en) * | 1981-05-15 | 1982-11-19 | Toshiba Ceramics Co Ltd | Quartz crucible for pulling up silicon single crystal |
CN87206316U (en) * | 1987-04-16 | 1987-12-30 | 清华大学 | Crucible with si3n4 coating |
JPH02172886A (en) * | 1988-12-26 | 1990-07-04 | Toshiba Ceramics Co Ltd | Semiconductor single crystal pulling up device |
JPH0751473B2 (en) * | 1988-12-26 | 1995-06-05 | 東芝セラミックス株式会社 | Carbon crucible for single crystal production |
JPH0597571A (en) | 1991-06-13 | 1993-04-20 | Toshiba Ceramics Co Ltd | Crucible for pulling up silicon single crystal |
JP3533416B2 (en) * | 1996-02-06 | 2004-05-31 | 三菱住友シリコン株式会社 | Single crystal pulling device |
JPH10316489A (en) * | 1997-05-12 | 1998-12-02 | Japan Steel Works Ltd:The | Mold for one direction solidification device and its production |
JPH11209133A (en) * | 1998-01-23 | 1999-08-03 | Mitsubishi Materials Corp | Transparent silica glass body and its production |
JP3981538B2 (en) | 2001-07-27 | 2007-09-26 | トーカロ株式会社 | Silicon holding container and manufacturing method thereof |
-
2005
- 2005-04-26 PL PL05740520T patent/PL1745164T3/en unknown
- 2005-04-26 AT AT05740520T patent/ATE398196T1/en active
- 2005-04-26 ES ES05740520T patent/ES2306141T3/en active Active
- 2005-04-26 JP JP2007509835A patent/JP5059602B2/en not_active Expired - Fee Related
- 2005-04-26 EP EP05740520A patent/EP1745164B1/en not_active Not-in-force
- 2005-04-26 UA UAA200612586A patent/UA87842C2/en unknown
- 2005-04-26 DE DE602005007484T patent/DE602005007484D1/en active Active
- 2005-04-26 TW TW094113170A patent/TWI361174B/en not_active IP Right Cessation
- 2005-04-26 US US11/587,081 patent/US7378128B2/en not_active Expired - Fee Related
- 2005-04-26 CN CN2005800134467A patent/CN1946881B/en not_active Expired - Fee Related
- 2005-04-26 RU RU2006140280/15A patent/RU2355832C2/en not_active IP Right Cessation
- 2005-04-26 MX MXPA06012509A patent/MXPA06012509A/en active IP Right Grant
- 2005-04-26 WO PCT/BE2005/000055 patent/WO2005106084A1/en active IP Right Grant
-
2006
- 2006-10-26 KR KR1020067022285A patent/KR101213928B1/en active IP Right Grant
- 2006-11-28 NO NO20065496A patent/NO339723B1/en not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3660075A (en) * | 1969-10-16 | 1972-05-02 | Atomic Energy Commission | CRUCIBLE COATING FOR PREPARATION OF U AND P ALLOYS CONTAINING Zr OR Hf |
US3746569A (en) * | 1969-11-18 | 1973-07-17 | Siemens Ag | Silicon nitride coating on quartz walls for diffusion and oxidation reactors |
US4741925A (en) * | 1987-09-14 | 1988-05-03 | Gte Products Corporation | Method of forming silicon nitride coating |
US5431869A (en) * | 1993-01-12 | 1995-07-11 | Council Of Scientific & Industrial Research | Process for the preparation of polycrystalline silicon ingot |
US6841210B2 (en) * | 2000-05-31 | 2005-01-11 | Heraeus Quarzglas Gmbh & Co., Kg | Multilayer structured quartz glass crucible and method for producing the same |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070089642A1 (en) * | 2005-10-21 | 2007-04-26 | Esk Ceramics Gmbh & Co. Kg | Durable hard coating containing silicon nitride |
US8012252B2 (en) * | 2005-10-21 | 2011-09-06 | Esk Ceramics Gmbh & Co., Kg | Durable hard coating containing silicon nitride |
US20090159230A1 (en) * | 2006-08-30 | 2009-06-25 | Kyocera Corporation | Mold Forming and Molding Method |
US8431070B2 (en) * | 2006-08-30 | 2013-04-30 | Kyocera Corporation | Mold forming and molding method |
US20090277377A1 (en) * | 2008-05-07 | 2009-11-12 | Covalent Materials Corporation | Crucible for melting silicon and release agent used to the same |
EP2486173A4 (en) * | 2009-10-06 | 2017-05-31 | LG Siltron Inc. | Quartz crucible and method of manufacturing the same |
US9625213B2 (en) * | 2011-08-31 | 2017-04-18 | 3M Innovative Properties Company | Silicon-nitride-containing separating layer having high hardness |
US20140272748A1 (en) * | 2011-08-31 | 2014-09-18 | Esk Ceramics Gmbh & Co. Kg | Silicon-nitride-containing interlayer of great hardness |
US20160230305A1 (en) * | 2013-09-16 | 2016-08-11 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Substrate for solidifying a silicon ingot |
US20160222542A1 (en) * | 2013-09-16 | 2016-08-04 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Substrate with low-permeability coating for the solidification of silicon |
US10023972B2 (en) * | 2013-09-16 | 2018-07-17 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Substrate for solidifying a silicon ingot |
US10287703B2 (en) * | 2013-09-16 | 2019-05-14 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Substrate with low-permeability coating for the solidification of silicon |
GB2550415A (en) * | 2016-05-18 | 2017-11-22 | Rec Solar Pte Ltd | Silicon ingot growth crucible with patterned protrusion structured layer |
US20200010978A1 (en) * | 2016-05-18 | 2020-01-09 | Rec Solar Pte. Ltd. | Silicon ingot growth crucible with patterned protrusion structured layer |
CN109955154A (en) * | 2019-04-15 | 2019-07-02 | 徐州协鑫太阳能材料有限公司 | A kind of processing method of crucible surface roughness |
CN110000708A (en) * | 2019-04-15 | 2019-07-12 | 徐州协鑫太阳能材料有限公司 | A method of transformation crucible roughness |
Also Published As
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MXPA06012509A (en) | 2007-01-31 |
UA87842C2 (en) | 2009-08-25 |
RU2355832C2 (en) | 2009-05-20 |
RU2006140280A (en) | 2008-05-27 |
JP5059602B2 (en) | 2012-10-24 |
TWI361174B (en) | 2012-04-01 |
ATE398196T1 (en) | 2008-07-15 |
NO339723B1 (en) | 2017-01-23 |
KR20070004901A (en) | 2007-01-09 |
PL1745164T3 (en) | 2008-11-28 |
ES2306141T3 (en) | 2008-11-01 |
KR101213928B1 (en) | 2012-12-18 |
CN1946881A (en) | 2007-04-11 |
EP1745164A1 (en) | 2007-01-24 |
US7378128B2 (en) | 2008-05-27 |
WO2005106084A1 (en) | 2005-11-10 |
EP1745164B1 (en) | 2008-06-11 |
NO20065496L (en) | 2006-11-28 |
CN1946881B (en) | 2010-06-09 |
TW200540130A (en) | 2005-12-16 |
JP2007534590A (en) | 2007-11-29 |
DE602005007484D1 (en) | 2008-07-24 |
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